U.S. patent number 4,391,726 [Application Number 06/274,126] was granted by the patent office on 1983-07-05 for detergent composition containing low levels of amine oxides.
This patent grant is currently assigned to The Procter & Gamble Company. Invention is credited to Robertus J. C. Koster.
United States Patent |
4,391,726 |
Koster |
July 5, 1983 |
Detergent composition containing low levels of amine oxides
Abstract
Detergent compositions having enhanced soil release and cleaning
properties include from 0.1%-1.5% amide oxide having at least one
long chain group and may include peroxybleach and detergent
builder, and provide an alkaline laundry pH.
Inventors: |
Koster; Robertus J. C.
(Grimbergen, BE) |
Assignee: |
The Procter & Gamble
Company (Cincinnati, OH)
|
Family
ID: |
10517647 |
Appl.
No.: |
06/274,126 |
Filed: |
June 16, 1981 |
Foreign Application Priority Data
|
|
|
|
|
Nov 28, 1980 [GB] |
|
|
8038306 |
|
Current U.S.
Class: |
510/299; 510/300;
510/305; 510/306; 510/320; 510/321; 510/341; 510/350; 510/441;
510/443; 510/503 |
Current CPC
Class: |
C11D
1/75 (20130101) |
Current International
Class: |
C11D
1/75 (20060101); C11D 007/18 () |
Field of
Search: |
;252/99,102,528,527,547,546 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Childs; Sadie L.
Claims
I claim:
1. A particulate laundry detergent composition having enhanced soil
release and cleaning properties comprising:
(a) from about 2% to about 25% by weight of a surface-active agent
selected from the group consisting of anionic, nonionic,
zwitterionic, and ampholytic detergents and mixtures thereof;
and
(b) from 0.25-0.75% of an amine oxide having the formula ##STR3##
wherein R is an alkyl or alkenylgroup having 10 to 22 carbon atoms,
the R.sub.1 's which are identical or different are selected from
C.sub.1-4 alkyl, ethylene oxide and propylene oxide, n is an
integer from 1 to about 6, m is an integer from 0 to about 6, p is
0 or 1, x, y, and z are each 1 for alkylsubstituents, and integers
in the range from 1 to 10 for ethylene oxide or propylene oxide
substituents such that the sum of (x+y+z) is not greater than
25,
(c) from about 3% to about 50% by weight of a peroxybleach
compound; and
(d) from about 1% to about 50% by weight of a detergent
builder;
whereby a 1% aqueous solution of the composition, measured at
20.degree. C., has a pH in the range from about 8.5 to about
11.
2. The composition in accordance with claim 1 wherein the detergent
builder is present in an amount from about 10% to about 45% by
weight.
3. The detergent composition in accordance with claim 1 which in
addition contains from 0.01% to 10% of a detergent suds
regulant.
4. The detergent composition in accordance with claim 2 wherein the
detergent builder is a mixture of
(i) a water-soluble detergent builder selected from the group
consisting of the water-soluble salts of nitrilotriacetic acid,
polyphosphates and citrates; and
(ii) a synthetic crystalline water-insoluble aluminosilicate
builder material selected from the group consisting of zeolite A,
zeolite X and zeolite P(B), said aluminosilicate material
containing at least 10% by weight of the silicate of water of
hydration and having a particle size diameter in the range from 0.5
micron to 30 microns;
whereby the weight ratio of the water-soluble detergent builder:
water-insoluble aluminosilicate builder is in the range from about
4:1 to about 1:4.
5. The composition in accordance with claim 1, wherein the amine
oxide is selected from the group consisting of N--C.sub.12-14
-coconutalkyl-N,N-dimethyl N-amine oxide; N-tallow C.sub.16-18
-alkyl-N,N',N-tri-(2-hydroxyethyl)-propylene-1,3-diamine-N,N'-dioxide;
N--C.sub.12-14
-alkyl-N,N',N'-tri-(2-hydroxyethyl)propylene-1,3-diamine-N,N'-dioxide;
N--C.sub.16-18 -tallow-alkyl-N,N-dimethyl-N-amine oxide;
N--C.sub.12-14 -coconut alkyl-N,N-di-(2-hydroxyethyl)-N-amine
oxide; or N--C.sub.16-18
-tallow-alkyl-N,N-di-(2-hydroxyethyl)-N-amine oxide.
6. The composition in accordance with claim 1 wherein m in the
structural formula for the amine oxide is 1.
7. The composition in accordance with claim 6 wherein the amine
oxide is N-hydrogenated
tallow-N,N',N'-tri(2-hydroxyethyl)-propylene-1,3-diamine-N,N'-dioxide.
8. The composition in accordance with claim 1, wherein the amine
oxide is present in an amount ranging from 0.25 to 0.35% by weight.
Description
TECHNICAL FIELD
This invention relates to detergent compositions containing low
levels of amine oxides. These amine oxides are substituted by at
least one long chain alkyl or alkenyl group. Preferred amine oxides
have at least two alkyl, especially methyl, or two alkylene oxide,
especially ethylene oxide, groups attached to the nitrogen atom(s).
These compositions produce an alkaline laundry liquor pH. These
compositions exhibit a broad range of remarkable textile treatment
benefits, particularly enhanced soil release and cleaning
properties.
There is a standing desire to improve textile cleaning and confer
further textile benefits through either the laundry treatment or
via the subsequent use, vs. the laundry treatment, of an additive
e.g. during the rinse.
U.S. Pat. No. 3,985,923, Basadur, issued Oct. 12, 1976, relates to
the application of renewable soil release finish during the rinsing
step from a dilute aqueous acidic solution. The release agent is a
copolymer based on a dibasic carboxylic acid and a glycolic
compound.
U.S. Pat. No. 3,962,152, Nicol, Hays, issued June 8, 1976 pertains
to the laundry treatment deposition of renewable soil release
finish to synthetic fabrics treated therewith. The soil release
finish consists of ethylene terephthalate and polyethylene oxide
terephthalate.
The performance benefits derived from the utilization of the like
additives are premised on the deposition of a releasable coating
onto the fiber from the laundry/rinsing step. The coating will be
rinsed off during the next laundry cycle, inclusive of the total
soil accumulated thereon, to thus provide a "non-alterated" degree
of cleaning.
Mono- and polyamine oxides have found widespread application in
detergent technology, mostly in a surfactant functionality.
Representative of this known state of the art are the following
references.
1. Dutch Patent Application No. 72-04495, Unilever N.V., relates to
alkali metal carbonate built detergent compositions containing a
binary surfactant combination, namely a nonionic surfactant and a
mono amine oxide which are normally used in a ratio of 1:3 to 3:1.
The total level of nonionic surfactant and amine oxide is in the
range from 5-25%.
2. British Pat. No. 1,007,343, The Procter & Gamble Company,
relates to surface-active diamine dioxides and compositions
composed thereof. These diamine dioxides are used in conventional
"surface-active" levels, i.e., at least 5% by weight of the
finished detergent compositions.
3. U.S. Pat. No. 3,531,526, The Procter & Gamble Company,
pertains to detergent diamine dioxides, prepared by oxidation of
the corresponding diamines. These oxides are used in detergents in
levels from 5-50%.
4. U.S. Pat. No. 4,133,779, The Procter & Gamble Company,
relates to detergent compositions containing a semi-polar nonionic
e.g. an amine oxide, in combination with an alkaline earth metal of
an anionic detergent. These compositions exhibit a neutral to
slightly alkaline pH. Exemplified levels of amine oxide in granular
detergents range from 1-15%.
5. U.S. Pat. No. 3,202,714, The Procter & Gamble Company,
pertains to oxy-containing tertiary amine oxide detergents and
detergent compositions containing them. These oxides are used in
granular and liquid detergents in levels frequently exceeding
10%.
The total prior art refers to the utilization of mostly monoamine
oxides in a conventional detergent functionality. It is widely
recognized that such amine oxides are good surfactants and indeed
have been utilized in commercial detergent executions. However, the
art is not suggestive of incidental textile benefits derivable from
utilizing unexpectedly low levels of the very components in a
non-surfactant functionality.
It is an object of the present invention to provide detergent
compositions containing a surface-active agent and low levels of
amine oxides; these compositions are capable of providing a broad
range of textile treatment benefits, particularly enhanced soil
release and cleaning properties.
SUMMARY OF THE INVENTION
The present invention comprises detergent compositions having
enhanced soil release and cleaning properties containing:
(a) from 2-60% surfactant selected from the group consisting of
anionic, nonionic, zwitterionic and ampholytic detergents and
mixtures thereof; and
(b) from 0.1%-1.5% of an amine oxide having the formula ##STR1##
wherein R is an alkyl or alkenyl group having 10 to 22 carbon
atoms, the R.sub.1 's which are identical or different are selected
from C.sub.1-4 alkyl, ethylene oxide and propylene oxide, n is an
integer from 1 to about 6, m is an integer from 0 to about 6, p is
0 or 1, x, y, and z are each 1 for alkyl substitutes and integers
in the range from 1 to 10 for ethylene oxide or propylene oxide
substituents such that the sum of (x+y+z) is not greater than 25,
whereby a 1% aqueous solution of the composition has an alkaline pH
(20.degree. C.).
In a preferred embodiment, the compositions herein are granular
compositions having an alkaline pH in the range from about 8.5-11
(1% aqueous solution, 20.degree. C.). In another preferred
embodiment, the compositions herein are homogeneous liquid
compositions having also an alkaline pH in the range from about
7.5-10.5 (1% aqueous solution, 20.degree. C.). Preferred granular
compositions herein are built detergent compositions wherein the
builder system is comprised of a water-soluble detergent builder or
a water-insoluble aluminosilicate detergent builder or a mixture
thereof.
DETAILED DESCRIPTION OF THE INVENTION
The detergent compositions of the present invention are defined in
three essential parameters:
(a) a surface-active agent;
(b) an amine oxide; and
(c) have an alkaline pH in 1% aqueous solution at 20.degree. C.
Optional ingredients can be added to provide various performance
and aesthetic benefits. The granular detergent executions of this
invention frequently comprise a peroxybleach ingredient, if desired
a peractivated system, in the usual levels, i.e., in the range from
about 3% to about 50% by weight, and a builder or co-builder system
as defined in more detail hereinafter.
Unless indicated to the contrary, the "percent" indications
hereinafter stand for "percent by weight".
The detergent compositions in accordance with this invention can be
in any conventional physical state inclusive of liquid pasty and
solid executions.
SURFACE-ACTIVE AGENT
The detergent compositions herein comprise, as a first essential
component, a surface-active agent selected from the group
consisting of anionic, nonionic, zwitterionic and ampholytic
detergents and mixtures thereof.
The surface-active agents normally represent from 2% to 60% of the
detergent composition.
The preferred granular detergents herein usually contain from about
2% to about 25%, preferably from about 5% to about 20% of organic
surface-active agents. Liquid executions of this invention
frequently contain surface-active agents in a level from about 5%
to about 50%, preferably from 15% to 40%.
Suitable organic surface-active agents herein can be represented by
active ingredients which are known to meet the requirements for use
in and/or have already been used in detergent compositions.
Exemplifying species for use herein can be selected from the group
of anionic, nonionic, ampholytic, zwitterionic, surfactants and
mixtures thereof.
Examples of suitable nonionic surfactants include:
(1) The polyethylene oxide condensates of alkyl phenols. These
compounds include the condensation products of alkyl phenols having
an alkyl group containing from about 6 to 12 carbons atoms in
either a straight chain or branched chain configuration, with
ethylene oxide, the said ethylene oxide being present in amounts
equal to 5 to 25 moles of ethylene oxide per mole of alkyl
phenol.
(2) The condensation products of aliphatic alcohols with ethylene
oxide. The alkyl chain of the aliphatic alcohol may either be
straight or branched and generally contains from about 8 to about
22 carbon atoms. Examples of such ethoxylated alcohols include the
condensation product of about 6 moles of ethylene oxide with 1 mole
of tridecanol, myristyl alcohol condensed with about 10 moles of
ethylene oxide per mole of myristyl alcohol, the condensation
product of ethylene oxide with coconut fatty alcohol wherein the
coconut alcohol is a mixture of fatty alcohols with alkyl chains
varying from 10 to 14 carbon atoms and wherein the condensate
contains about 6 moles of ethylene oxide per mole of alcohol, and
the condensation product of about 9 moles of ethylene oxide with
the above-described coconut alcohol.
(3) The condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylene
diamine. The condensation product frequently contains from about
40% to about 80% by weight of polyoxyethylene and has a molecular
weight of from about 5,000 to about 11,000.
Examples of suitable ampholytic synthetic detergents are sodium
3-(dodecyl-amino)-propionate, and sodium
3-(dodecylamino)propane-1-sulfonate.
Zwitterionic surfactants for use herein include
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate,
3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate, the
alkyl group being derived from tallow fatty alcohol;
3-(N,N-dimethyl-N-hexadecylammonio)propane-1-sulfonate;
3-(N,N-dimethyl-N-tetradecylammonio)propane-1-sulfonate; and
3-(N--N-dimethyldodecylammonio)-2-hydroxypropane-1-sulfonate.
Suitable anionic detergents include ordinary alkali metal soaps of
higher fatty acids containing from about eight to about 24 carbon
atoms and preferably from about 10 to about 20 carbon atoms.
Alkyl sulfonated or sulfated surfactants inclusive of alkyl benzene
sulfonates, in which the alkyl group contains from about 9 to about
20 carbon atoms in straightchain or branched-chain configuration,
e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and
2,477,383 (especially valuable are linear straight chain alkyl
benzene sulfonates in which the average of the alkyl groups is
about 11.8 carbon atoms and commonly abbreviated as C.sub.11.8
LAS); sodium alkyl glyceryl ether sulfonates, especially those
ethers of higher alcohols derived from tallow and coconut oil;
sodium coconut oil fatty acid monoglyceride sulfonates and sulfates
also represent a class of very useful anionic surface-active
agents.
Useful in this invention are also salts of
2-acyloxyalkane-1-sulfonic acids.
Typical examples of the 2-acyloxy-alkanesulfonates are described in
Belgium Pat. No. 650,323 issued July 9, 1963, U.S. Pat. No.
2,094,451 issued Sept. 28, 1937 to Guenther et al., and U.S. Pat.
No. 2,086,215 issued July 6, 1937 to DeGroote; these references are
hereby incorporated by reference.
.beta.-alkoxy alkane sulfonates can also be used. Specific examples
of .beta.-alkyloxy alkane sulfonates having low hardness (calcium
ion) sensitivity useful herein to provide superior cleaning levels
under household washing conditions include:
potassium-.beta.-methoxydecanesulfonate, sodium
2-methoxytridecanesulfonate, potassium 2-ethoxytetradecylsulfonate,
and sodium 2-isopropoxyhexadecylsulfonate.
Paraffin sulfonates containing a straight or branched chain,
saturated aliphatic hydrocarbon radical having from 8 to 24,
preferably 12 to 18, carbon atoms can also be used.
Other synthetic anionic detergents useful herein are alkyl ether
sulfates. These materials have the formula RO(C.sub.2 H.sub.4
O).sub.x SO.sub.3 M wherein R is alkyl or alkenyl of about 10 to
about 20 carbon atoms, x is 1 to 30, and M is a water-soluble
cation.
Suitable examples of alkyl ether sulfates are those comprising a
mixture of individual compounds, said mixture having an average
alkyl chain length of from about 12 to about 16 carbon atoms and an
average degree of ethoxylation of from about 1 to 4 moles of
ethylene oxide. Such a mixture also comprises from about 0 to 20%
by weight C.sub.12-13 compounds; from 60 to 100% by weight of
C.sub.14-15-16 compounds; from 0 to 20% by weight of C.sub.17-18-19
compounds; from about 3 to 30% by weight of compounds having a
degree of ethoxylation of 0; from about 45 to 90% by weight of
compounds having a degree of ethoxylation of from 1 to 4; from
about 10 to 25% by weight of compounds having a degree of
ethoxylation of from 4 to 8; and from about 0.1 to 15% by weight of
compounds having a degree of ethoxylation greater than 8.
.alpha.-Olefin sulfonate mixtures as described in U.S. Pat. No.
3,332,880, issued July 25, 1967, incorporated herein by reference,
can also be used.
THE AMINE OXIDE
A second essential component in the compositions herein is
represented by an amine oxide having the formula ##STR2## wherein R
is an alkyl or alkenylgroup having 10 to 22 carbon atoms, the
R.sub.1 's which are identical or different are selected from
C.sub.1-4 alkyl, ethylene oxide and propylene oxide, n is an
integer from 1 to about 6, m is an integer from 0 to about 6, p is
0 or 1, x, y, and z are each 1 for alkylsubstituents, and integers
in the range from 1 to 10 for ethylene oxide or propylene oxide
substituents such that the sum of (x+y+z) is not greater than
25.
This amine oxide component is used in a level from 0.1% to 1.5%,
preferably from 0.25% to 0.75%. Utilizing less than the minimum
levels will not provide anymore the inventive benefits, whereas
levels above the specified definition will not yield anymore
performance advantages but rather unexpectedly causes noticeable
cleaning performance negatives, particularly whiteness
deficiencies.
Suitable species of the amine oxide component for use herein
correspond to the general formula above wherein the individual
substituents can be varied as follows:
R: tallow C.sub.16-18 alkyl; coconut C.sub.12-14 alkyl; lauryl;
palmityl; stearyl; oleyl.
R.sub.1 : ethylene oxide; propylene oxide; methyl; ethyl.
n: 2, 3, 4.
m: 0, 1, or 2.
x,y, and z are each 1, 2, 3 or 4 and their sum is from 2 to 18.
Preferred amine oxides for use herein are defined by the following
substituents:
R: hydrogenated tallow C.sub.16-18 alkyl; coconut C.sub.12
-C.sub.14 alkyl.
R.sub.1 : ethylene oxide; methyl.
m: 0 or 1;
n: 3 (assuming m is different from 0).
x, y, z are each at least 1 and their sum is in the range from 2 to
12, for example 2, 3,7 and 12.
One particularly preferred class of amine oxide species is
represented by mono-amine oxides having the following
substituents.
m: 0.
R.sub.1 : methyl; ethyl; ethylene oxide.
R: coconut C.sub.12 -C.sub.14 alkyl.
x and y are both 1.
A specific example of this preferred class of mono-amine oxides is:
N--C.sub.12 --C.sub.14 coconut alkyl-N,N-dimethyl amine oxide.
Another particularly preferred class of amine oxide species is
represented by bis-amine oxides having the following
substituents.
m: 1
R: tallow C.sub.16 -C.sub.18 alkyl; palmityl; oleyl; stearyl.
R.sub.1 : ethylene oxide.
n: 2 or 3.
x, y, and z are each at least 1, and their sum is from 3 to 12. A
specific example of this preferred class of bis-amine oxides is:
N-hydrogenated C.sub.16 -C.sub.18 tallow
alkyl-N,N',N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine oxide.
ALKALINE SOLUTION
The compositions herein shall yield upon dissolution in water an
alkaline laundry liquor. Preferably, a 1% aqueous solution of
granular detergent compositions shall have an alkaline pH in the
range from about 8.5 to about 11, measured at 20.degree. C. A 1%
aqueous solution of liquid detergent compositions frequently has a
pH in the range from 7.5-10.5 (20.degree. C.). The pH can be
adjusted by known means inclusive of alkaline buffer substances
such as alkali hydroxides, ammonium hydroxide, amines and
substituted amines, such as mono-, di- and triethanolamines;
alkaline builder substances such as alkali metal carbonates,
alkalimetal phosphates and polyphosphates, citric acid and
alkalimetal silicates. The proper choice of suitable pH adjusting
agents shall of course take into account the physical
state--liquid, pasty, solid--of the composition and the relative
compatibility of the additional ingredients of a particular
composition. Such ingredient optimization and selection are
well-known routine measures, however.
OPTIONAL INGREDIENTS
As is well-known, detergent compositions vary in relation to the
physical state of the composition, the intended usage and the local
textile treatment needs inclusive of laundering habits. Solid,
granular detergent compostions frequently contain a peroxybleach
compound in an amount from about 3% to about 50%, preferably from
about 5% to about 35%. Suitable peroxybleach compounds are all
those which are known to be adapted for use in or have already been
used in detergent technology. Examples of such peroxybleaches
include the water-soluble alkali salts of perborate mono-hydrate,
perborate tetrahydrate, persulfates, persilicates, perphosphates,
and percarbonates. Organic oxygen-bleach activators can also
advantageously be used in oxygen-bleach containing detergent
executions of this invention. Examples of such activators include
phthalic anhydride, tetra-acetyl ethylene diamine, tetra-acetyl
methylene diamine and tetra-acetyl glycouril. Such activators are
frequently used in levels from about 0.2% to 15%, preferably from
1% to 4%. The weight ratios of the peroxybleach compound to the
activator is frequently in the range from about 10:1 to 2:1.
The detergent compositions of this invention further frequently
contain as an optional ingredient, a detergent builder in a level
from about 1% to about 50%. The non-solid detergent embodiments
frequently contain builder ingredients in levels up to 15%. The
solid detergents contain a detergent builder or a detergent builder
system in a level which is preferably in the range from about 10%
to about 45%. The builder component can be represented by all known
water-soluble and water-insoluble detergent builder
ingredients.
Non-limiting examples of suitable water-soluble, inorganic alkaline
detergency builder salts include the alkali metal carbonates,
borates, phosphates, polyphosphates, tripolyphosphates,
bicarbonates, silicates, and sulfates. Specific examples of such
salts include the sodium and potassium tetraborates, bicarbonates,
carbonates, tripolyphosphates, pyrophosphates, and
hexametaphosphates.
Examples of suitable organic alkaline detergency builder salts are:
(1) water-soluble amino polyacetates, e.g. sodium and potassium
ethylene diamine tetra-acetates, nitrilotriacetates, and
N-(2-hydroxyethyl)nitrilodiacetates; (2) water-soluble salts of
phytic acid, e.g. sodium and potassium phytates; (3) water-soluble
polyphosphonates, including sodium, potassium and lithium salts of
ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium, and
lithium salts of methylenediphosphonic acid and the like.
Additional organic builder salts useful herein include the
polycarboxylate materials described in U.S. Pat. No. 2,264,103,
including the water-soluble alkali metal salts of mellitic acid.
The water-soluble salts of polycarboxylate polymers and copolymers
such as are described in U.S. Pat. No. 3,308,067, incorporated
herein by reference, are also suitable herein. Citric acid
detergent builders can advantageously be used in liquid
detergents.
It is to be understood that while the alkali metal salts of the
foregoing inorganic and organic polyvalent anionic builder salts
are preferred for use herein from an economic standpoint, the
ammonium, alkanolammonium (e.g. triethanolammonium,
diethanolammonium and monoethanolammonium) and other water-soluble
salts of any of the foregoing builder anions can be used.
Mixtures of organic and/or inorganic builders can be used herein.
One such mixture of builders is disclosed in Canadian Pat. No.
755,038, e.g., a ternary mixture of sodium tripolyphosphate,
trisodium nitrilotriacetate, and trisodium
ethane-1-hydroxy-1,1-diphosphonate.
Another type of detergency builder material useful in the present
invention comprises a water-soluble material capable of forming a
water-insoluble reaction product with water hardness cations,
preferably in combination with a crystallization seed which is
capable of providing growth sites for said reaction product.
Specific examples of materials capable of forming the
water-insoluble reaction product include the water-soluble salts of
carbonates, bicarbonates, sesquicarbonates, silicates, aluminates
and oxalates. The alkali metal, especially sodium, salts of the
foregoing materials are preferred for convenience and economy.
Preferred crystallization seed materials are calcium carbonate,
calcium oxide and calcium hydroxide. Such "seeded builder"
compositions are fully disclosed in British Patent Specification
No. 1,424,406, incorporated herein by reference.
Non-seeded precipitating builder systems employing pyrophosphates
or mixtures thereof with orthophosphates are also useful herein.
Precipitating pyrophosphate and orthopyrophosphate builder systems
are disclosed in German Patent Applications OLS Nos. 25 42 704 and
26 05 052 published Apr. 15 and Aug. 16, 1976, respectively, which
are specifically incorporated herein by reference.
Suitable examples of water-insoluble detergent builders are
selected from the group consisting of zeolites A, X, or P(B), or
mixtures thereof, having a particle size diameter of from about
0.01 micron to about 25 microns and containing at least 10% water
of hydration, and amorphous hydrate aluminosilicate material of the
empirical formula: M.sub.z (zAlO.sub.2.ySiO.sub.2) wherein M is
sodium, potassium ammonium, z is from about 0.5 to about 2, y is 1,
said material having a particle size diameter of less than about
100 microns, a magnesium ion exchange capacity of at least about 50
milligrams equivalents of CaCO.sub.3 hardness per gram of anhydrous
aluminosilicate, and a Mg.sup.++ exchange rate of at least about 1
grain/gallon/minute/gram/gallon, and mixtures thereof.
The preferred synthetic crystalline aluminosilicate materials for
use herein commonly known as Zeolites A, X, and P(B) should contain
at least 10% water of hydration and should have a particle size
diameter of from about 0.5 micron to about 30 microns, more
preferably from about 0.5 micron to about 10 microns.
Aluminosilicate materials are more fully described in U.S. Pat. No.
4,096,081, Phenicie et al., issued June 20, 1978, and German Pat.
No. 27 04 003, Ohren, published on Aug. 18, 1977, the disclosures
of which are incorporated herein by reference. The amorphous
aluminosilicate materials suitable for use herein are fully
described in U.S. Pat. No. 4,180,485, Llenado, published Dec. 25,
1979, incorporated herein by reference.
The water-insoluble detergent builders are frequently and
preferably utilized in the granular compositions herein in
conjunction with a water-soluble detergent cobuilder ingredient in
a weight ratio of aluminosilicate:water-soluble detergent cobuilder
of from 4:1 to 1:4. Suitable examples of preferred water-soluble
cobuilder ingredients are represented by the water-soluble salts of
nitrilotriacetic acid, polyphosphates e.g. tripolyphosphates, and
citrates. The cations of these cobuilders can e.g. be represented
by alkalimetal ions, sodium, potassium, lithium, and by organic
ions such as amines, substituted amines (alkanolamines) and
ammonium ions.
In addition to the components described hereinbefore, the
compositions of this invention can comprise a series of
supplementary components to perfect and complement the benefits
derived from the compositions herein. These additional components
include brighteners, dyes, perfumes, bactericides, processing aids,
anti-oxidants, corrosion inhibitors, enzymes suds regulants and so
on.
It may be desirable to add a copolymer of a (1) vinyl compound
having the general formula RCH.dbd.CHR wherein one R represents a
hydrogen atom and the other R represents an alkyl radical
containing from one to about 4 carbon atoms; and (2) maleic
anhydride. The copolymeric vinyl ingredient is normally used in an
amount from about 0.1% to about 6%, preferably from 0.25% to 4%.
Specific examples of these copolymeric ingredients include a
water-soluble acid, an alkali-metal salt of that acid, an ester, or
a C.sub.1-2 alkyl- or alkylolamide of a maleic anhydride-vinyl
C.sub.1-4 alkyl ether copolymer. The specific viscosity of, for
example, the maleic anhydride-vinyl C.sub.1-4 alkyl ether,
preferably methylether, copolymer for use herein normally varies
between 0.1 and 6, most preferably between 0.2 and 5.0. The
(molecular) monomer ratio (maleic:vinylalkylether) is preferably in
the range from 2:1 to 1:2. The specific viscosity is defined by
measuring the viscosity of the solution of 1 g of the anhydride
copolymer in 100 ml methylethylketone at 25.degree. C. in a series
100 CANNON-FENSKE viscosity meter. The copolymeric component can
serve as slurry processing aid to thus provide a detergent product
having improved physical properties including flowability.
Another optional ingredient is a mixture of alkoxylated mono- and
diesters of phosphoric acid. This mixture which is normally used in
an amount from 0.5% to 20% by reference to the sum of the
surface-active agents, is particularly useful in detergent
compositions containing, in part or solely, nonionic surface-active
agents. These phosphoric esters are preferably represented by
alkoxylated fatty alcohols having from 10 to 22 carbon atoms with 2
to 15 moles ethylene oxide or propylene oxide. The weight ratio of
monophosphoric esters to diphosphoric esters is usually in the
range from 6:1 to 3:1, preferably 4:1.
It may be desirable, especially if nonionic surfactants are
incorporated by slurrying and subsequent spray-drying, to add to
the crutcher from 0.01% to 10%, expressed by reference to the
nonionic surfactant of, an anti-oxidant. Suitable examples of
anti-oxidant materials are disclosed in German Patent Application
DAS No. 16 17 209. A preferred anti-oxidant material is
4,4'-thiobis(6-tert-butyl-m-cresol).
The detergent compositions can additionally contain an enzymatic
ingredient. Proteases, amylases and lipases can be added in an
amount from 0.001% to about 5% to augment and aid in the cleaning
activity of the detergent compositions herein. Preferred
proteolytic enzymes are disclosed in Belgian Pat. No. 775.854, to
EYMERY et al., granted May 26, 1972.
The detergent compositions of this invention frequently comprise a
suds regulant in a level of 0.01%-10%.
Suitable suds regulants are well-known in detergent technology and
most of these can easily be used in combination with the claimed
technology.
Conventional detergent suds regulants which can be used include
saturated fatty acids especially those having 16 to 24 carbon atoms
in the alkylchain, nonionic suds regulants and mixtures thereof.
Another class of well-known suds regulants are silicones,
preferably silanated silicones in admixture with microcrystalline
waxes. Mixtures of low levels of silicones (0.01-0.2%) and/or fatty
acids (0.2-2%) are known to be suitable for use in the liquid
executions of this invention.
Preferred suds regulants containing a separately processed
detergent additive on basis of a water-insoluble liquid
hydrocarbon, an adjunct material preferable a solid hydrocarbon,
and a hydrophobic silica are described in U.S. Pat. No. 4,192,761,
Peltre and Lafleur, issued Mar. 11, 1980, incorporated herein by
reference. These liquid hydrocarbon-containing regulants are
preferably used in granular executions.
The following examples illustrate the invention and facilitate its
understanding.
EXAMPLE I
A detergent composition was prepared having the following
formulation.
______________________________________ Example (% by Composition
weight) INGREDIENTS A I ______________________________________
Linear dodecylbenzene sulfonate sodium salt 5.6 5.6 Tallow alcohol
sulfate sodium salt 2.4 2.4 Sodium tripolyphosphate 24.0 24.0
Sodium silicate solids (SiO.sub.2 :Na.sub.2 O = 1.6) 6.0 6.0
Carboxymethylcellulose 1.0 1.0 Copolymer of maleic anhydride and
methyl vinyl ether 1.0 1.0 Sodium sulfate 18.2 17.85 Moisture 7.0
7.0 ______________________________________
A series of spray-drying sensitive ingredients were added to the
above base-powder by dry-mixing, namely:
______________________________________ perborate tetrahydrate 32.0
32.0 enzyme 0.3 0.3 minors inclusive of perfume 2.5 2.5 suds
regulant particles having the composition of Example I of U.S. Pat.
No. 4,192,761 0.3 0.3 ______________________________________
0.35% of N-hydrogenated
tallow-N,N',N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine-N,N'-dioxide
was sprayed onto the mixture of the base-powder and the
spray-drying sensitive ingredients.
The detergent compositions were used for comparative laundry tests
in a Miele W 421 washing machine.
Terry, undershirt and muslin cotton tracers were used to measure
the comparative whiteness maintenance performance after 4
cumulative cycles.
Testing parameters were: 90.degree. C. heat-up cycle; pre-wash step
and main-wash step using a product concentration of 0.9% in city
water with an average water hardness of about 3 mmoles/l; ratio
Ca/Mg=5:1; laundering treatment in presence of 3 kg soiled
clothes.
After having been subjected to the above washing treatment (4
cumulative cycles) the dried whiteness maintenance tracers were
visually graded by two expert judges thereby using a 0-4 scale
whereby:
0=see no difference between the swatches
1=believe there is a difference between the swatches
2=there is a difference between the swatches
3=am sure there is a difference between the swatches
4=very important difference between the swatches.
The whiteness maintenance readings were pooled and averaged on 4
replicates with the following results. The swatches treated with
composition A were used for reference purposes:
______________________________________ Tracer Example I
______________________________________ Terry + 1.3 Undershirt + 1.0
Muslin + 1.0 ______________________________________ +means that
example I is preferred over composition A.
These testing results confirm the consistent superiority of example
I in accordance with this invention versus prior art composition
A.
Substantially identical results are obtained from the compositions
of Example I wherein the tallowdiaminedioxide is substituted by a
an equivalent level of: N--C.sub.12-14
-alkyl-N,N',N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine-N,N'-dioxide;
N-palmityl-N,N',N'-hepta-(2-hydroxyethyl)-ethylene-1,2-diamine-N,N'-dioxid
e; N--C.sub.16-18 -tallowalkyl-N,N-dimethyl-N-amine oxide;
N--C.sub.12-14 -coconut alkyl-N,N-di-(2-hydroxyethyl)-N-amine
oxide; or N--C.sub.16-18
-tallowalkyl-N,N-di-(2-hydroxyethyl)-N-amine oxide.
EXAMPLE II
A detergent composition was prepared having the following
composition:
______________________________________ Composition Example
INGREDIENTS A II ______________________________________ Linear
dodecylbenzene sulfonate sodium salt 5.6 5.6 Tallow alcohol sulfate
sodium salt 2.4 2.4 Sodium tripolyphosphate 24.0 24.0 Sodium
silicate solids (SiO.sub.2 :Na.sub.2 O = 1.6) 6.0 6.0
Carboxymethylcellulose 1.0 1.0 Copolymer of maleic anhydride and
methyl vinyl ether 1.0 1.0 Sodium sulfate 18.2 17.85 Moisture 7.0
7.0 C.sub.12 -C.sub.14 alkyl dimethylamine oxide -- 0.35 Perborate
tetrahydrate 32.0 32.0 Enzyme 0.3 0.3 Minors inclusive of perfume
2.5 2.5 ______________________________________
The amine oxide was incorporated into the crutcher. The
spray-drying sensitive ingredients were added to the base-powder by
dry-mixing.
Testing conditions were identical to those described in Example 1
hereinbefore.
Whiteness maintenance readings were pooled and averaged on 4
replicates with the following results. Swatches treated with
composition A were used for reference purposes.
______________________________________ Tracer Example I
______________________________________ Terry + 1.00 Undershirt +
0.80 ______________________________________
EXAMPLE III
Detergent compositions were prepared by using the di-aminedioxide
of Example I in accordance with the technique set forth in that
example.
______________________________________ Example Example Ingredients
I III ______________________________________ Diamine-dioxide 0.35
2.00 Linear dodecylbenzene sulfonate sodium salt 5.6 5.6 Tallow
alcohol sulfate sodium salt 2.4 2.4 Sodium tripolyphosphonate 24.0
24.0 Sodium silicate solids (SiO.sub.2 :Na.sub.2 O = 1.6) 6.0 6.0
Carboxymethylcellulose 1.0 1.0 Copolymer of maleic anhydride and
methyl vinyl ether 1.0 1.0 Perborate tetrahydrate 32.0 32.0 Enzyme
0.3 0.3 Minors inclusive of perfume 2.5 2.5 Sodium sulfate,
moisture ______________________________________
Testing conditions were identical to those described in Example I
hereinbefore.
Whiteness maintenance leadings were pooled and averaged on 4
replicates with the following results. Swatches treated with
Composition I were used for reference purposes.
______________________________________ Tracer Example III
______________________________________ Terry - 3.00 Undershirt -
3.20 Muslin - 2.00 ______________________________________
These comparative results confirm the performance superiority and
level criticality of a detergent composition containing the claimed
amine-dioxides.
EXAMPLE IV
Liquid detergent compositions were prepared having the following
compositions:
______________________________________ Composition Example
Ingredients B IV ______________________________________ Linear
dodecylbenzene sulfonate sodium salt 18.0 18.0 Condensation product
of 8 moles of ethylene oxide and one mole of a C12-C15 alcohol 5.0
5.0 Sodium citrate 10.0 10.0 Sodium silicate 0.7 0.7 Sodium xylene
sulfonate 5.5 5.5 Carboxymethyl cellulose 0.5 0.5 N--hydrogenated
tallow-N,N',N'--tri- (2-hydroxyethyl)-propylene
diamine-1,3-N,N'--dioxide -- 0.35 Water balance balance
______________________________________
The above compositions were used for comparative laundry tests in a
Miele W421 washing machine.
Terry, undershirt, muslin and polyester cotton tracers were used to
measure the comparative whiteness maintenance performance after 4
cumulative cycles in the way described in Example I.
Testing parameters were: 60.degree. C. heat-up cycle; mainwash only
step using a product concentration of 0.75% in city water with an
average water hardness of about 3 mmoles/l.; ratio Ca/Mg: 5:1;
laundering treatment in presence of 3 kg soiled clothes.
The whiteness maintenance readings were pooled and averaged on 4
replicates with the following results. The swatches treated with
prior art composition B were used as a reference.
______________________________________ Tracer Example IV
______________________________________ Terry + 1.4 Undershirt + 0.9
Polycotton + 0.9 ______________________________________
EXAMPLE V
A detergent composition was prepared having the composition of
Example II, except for the C.sub.12 -C.sub.14 dimethyl amine oxide
which was used at a level of 0.5%, the balance being sodium
sulfate.
The testing parameters were: 60.degree. C. heat-up cycle; mainwash
only using a product concentration of 0.7%; city water with an
average water hardness of about 4.2 mmoles/l.; ratio Ca/Mg=5:1;
laundering treatment in presence of 3 kg soiled clothes.
The whiteness maintenance readings were pooled and averaged on 4
replicates with the following results. The swatches treated with
prior art composition A were used as a reference.
______________________________________ Tracer Example V
______________________________________ Terry + 1.8 Undershirt + 1.4
Muslin + 1.8 Polycotton + 1.3
______________________________________
These data confirm that the compositions of this invention provide
truly superior performance upon use in a up-to-60.degree. C. (as
compared to up-to-the-boil) laundering method.
Heavy duty liquid detergents are prepared by mixing the listed
ingredients.
______________________________________ Examples (% by Weight)
Ingredients VI VII ______________________________________ Linear
dodecylbenzene sulfonic acid 14 17 Condensate of 1 mole aliphatic
C12-C15 alcohol with 7 moles of ethylene oxide 15 15 Lauric acid 10
8 Oleic acid 5 7 Triethanolamine 5 6 Sodium hydroxide to adjust pH
to 8 Propanediol-1,2 10 10 Citric acid 0.2 0.2 Diethylene triamine
penta methylene phosphonate 0.6 0.6 Silicone 0.2 0.2 Sodium formate
1.0 1.0 Proteolytic enzyme (Maxatase) 0.2 0.2 N--C.sub.12-14
-coconutalkyl-N,N-- dimethyl N--amine oxide 0.6 -- N--tallow
C.sub.16-18 alkyl-N,N',N'--tri- (2-hydroxyethyl)-propylene-
1,3-diamine-N,N'--dioxide -- 0.5 Water + minors balance to 100
______________________________________
The compositions VI and VII of this invention exhibit excellent
textile cleaning and whiteness maintenance properties.
* * * * *